S-caprolactam

Nylon-6. Nylon-6—clay nanometer composites using montmorillonite clay intercalated with 12-aminolauric acid have been produced (37,38). When mixed with S-caprolactam and polymerized at 100°C for 30 min, a nylon clay—hybrid (NCH) was produced. Transmission electron microscopy (tern) and x-ray diffraction of the NCH confirm both the intercalation and molecular level of mixing between the two phases. The benefits of such materials over ordinary nylon-6 or nonmolecularly mixed, clay-reinforced nylon-6 include increased heat distortion temperature, elastic modulus, tensile strength, and dynamic elastic modulus throughout the —150 to 250°C temperature range. 

Developments in aliphatic isocyanates include the synthesis of polymeric aliphatic isocyanates and masked or blocked diisocyanates for appflcafions in which volatility or reactivity ate of concern. Polymeric aliphatic isocyanates ate made by copolymerizing methacrylic acid derivatives, such as 2-isocyanatoethyl methacrylate, and styrene [100-42-5] (100). Blocked isocyanates ate prepared via the reaction of the isocyanate with an active hydrogen compound, such as S-caprolactam, phenol [108-95-2] or acetone oxime. 

Enzymatic hydrolysis is also used for the preparation of L-amino acids. Racemic D- and L-amino acids and their acyl-derivatives obtained chemically can be resolved enzymatically to yield their natural L-forms. Aminoacylases such as that from Pispergillus OTj e specifically hydrolyze L-enantiomers of acyl-DL-amino acids. The resulting L-amino acid can be separated readily from the unchanged acyl-D form which is racemized and subjected to further hydrolysis. Several L-amino acids, eg, methionine [63-68-3], phenylalanine [63-91-2], tryptophan [73-22-3], and valine [72-18-4] have been manufactured by this process in Japan and production costs have been reduced by 40% through the appHcation of immobilized cell technology (75). Cyclohexane chloride, which is a by-product in nylon manufacture, is chemically converted to DL-amino-S-caprolactam [105-60-2] (23) which is resolved and/or racemized to (24)... 

The only other nitroparaffin manufactured on a large scale was nitrocyclohexane [1122-60-7] made by Hquid-phase nitration of cyclohexane. Nitrocyclohexane was the starting material for S-caprolactam via reduction to cyclohexanone oxime. This process has been superseded by other, more efficient processes (see Caprolactam). Nitrocyclohexane is not being produced ia large quantities for either captive use or sale. 

Ingredients. Nylon-6 is produced commercially from caprolactam [105-60-2] which is the most important lactam industrially. AH industrial production processes for caprolactam are multistep and produce ammonium sulfate [7783-20-2] or other by-products. Approximately 95% of the world s caprolactam is produced from cyclohexanone oxime [100-64-1] via the Beckmann rearrangement (144). The starting material for cyclohexanone can be... 

In Europe, 1. G. Earbenindustrie decided to develop nylon-6 that had been synthesized from S-caprolactam using an aminocaproic acid catalyst (1) and commercially introduced as Pedon L in 1940 (11,12). 1. G. Earbenindustrie had evaluated over 3000 polyamide constituents without finding an improvement over nylon-6 and nylon-6,6 (13). In Italy, Societa Rhodiaceta started making nylon-6,6 in 1939. In the United Kingdom, ICl and Courtaulds formed British Nylon Spinners in 1940 and started to manufacture nylon-6,6 in 1941. 

Hexamethylenediamine [124-09-4] and adipic acid [124-04-9] are used in the commercial production of nylon-6,6 and S-caprolactam [105-60-2] is used for nylon-6 (see also Adipic acid Caprolactam). 

Nylon-6 is the polyamide formed by the ring-opening polymerization of S-caprolactam. The polymerization of S-caprolactam can be initiated by acids, bases, or water. Hydrolytic polymerization initiated by water is often used in industry. The polymerization is carried out commercially in both batch and continuous processes by heating the monomer in the presence of 5—10% water to temperatures of 250—280°C for periods of 12 to more than 24 h. The chemistry of the polymerization is shown by the following reaction sequence. 

Block, Gr ft, ndSta.r Copolymers. A host of copolymers of these types have been prepared. They iaclude block copolymers from S-caprolactam and PTMEG as well as block copolymers from PTHF and other cationicaHy polymerizable heterocycles, including... 

HO—R—COOH, or an amino acid, H2N—R—COOH. In some cases, such monomers self-condense to a cycHc stmcture, which is what actually polymerizes. For example, S-caprolactam (1) can be thought of as the self-condensation product of an amino acid. Caprolactam undergoes a ring-opening polymerization to form another... 

Caprolactam [105-60-2] (2-oxohexamethyleiiiiriiQe, liexaliydro-2J -a2epin-2-one) is one of the most widely used chemical intermediates. However, almost all of the aimual production of 3.0 x 10 t is consumed as the monomer for nylon-6 fibers and plastics (see Fibers survey Polyamides, plastics). Cyclohexanone, which is the most common organic precursor of caprolactam, is made from benzene by either phenol hydrogenation or cyclohexane oxidation (see Cyclohexanoland cyclohexanone). Reaction with ammonia-derived hydroxjlamine forms cyclohexanone oxime, which undergoes molecular rearrangement to the seven-membered ring S-caprolactam. 

Reaction-Injection Molding and Reactive Casting. Reaction-iajection molding (RIM) (22) and reactive casting (23) have been demonstrated on nylon-6, which is polymerized by catalytic ring opening and linear recondensation of S-caprolactam (qv) (24). 

The preparation of nylon resins from lactam precursors involves ring opening, which is facihtated by a controlled amount of water in the reaction mixture. The salt complex condenses internally to produce the polyamide (57). The synthesis of nylon-6 [25038-54-4] from S-caprolactam is as follows ... 

Ammonolysis is the preferred route currently in use at the DuPont Company for the depolymerization of nylon-6,6 carpet waste. McKinney13 has described the reaction of nylon-6,6 and nylon-6 mixtures with ammonia at temperatures in the range of 300-350°C at a pressure of about 68 atm in the presence of an ammonium phosphate catalyst to form a mixture of nylon-6,6 and nylon-6 monomers (HMD A, A A, and s-caprolactam) and adiponitrile, 5-cyanovaleramide, 6-aminocapronitrile, and 6-aminocaproamide. 

Polyamides, commonly known as nylons, may safely be used to produce articles intended for application in processing, handling, and packaging of food, including for products intended to be cooked directly in their packages. Nylon resins are manufactured by condensation of hexyamethylenediamine and adipic acid (nylon 66) or sebacic acid (nylon 610), by the polymerization process, e.g., of co-laurolactam (nylon 12), or by condensation and polymerization, e.g., nylon 66 salts and s-caprolactam. 

Table 11.3 shows the main uses of cyclohexane. Adipic acid is used to manufacture nylon 6,6, the major nylon used currently in the U.S. Caprolactam is the monomer for nylon 6, for which there is a growing market. 

Pyrrolidone is a lactone used for the production of nylon-4. This reactant may be produced by the reduction ammoniation of maleic anhydride. s-Caprolactam, used in the production of nylon-6, may be produced by the Beckman rearrangement of cyclohexanone oxime (structure 17.11). The oxime may be produced by the catalytic hydrogenation of nitrobenzene, the photolytic nitrosylation of cyclohexane (structure 17.9), or the reaction of cyclohexanone and hydroxylamine (structure 17.10). Nearly one-half of the production of caprolactam is derived from phenol. 

For the worldwide production of s-caprolactam, see http //unit.aist.go.jp/rics/event04/ 040624ws/B oero.pdf. 

Gui et reported the Beckmann rearrangement of ketoximes using a sulfonyl chloride-containing imidazolium-based TSIL to furnish s-caprolactam, which was immiscible in the IL, resulting in easy separation. Similar ILs were... 

Nitroalkanes. A process was developed and operated for a time for the manufacture of s-caprolactam based on the nitration of cyclohexane.197 Nitrocyclohexane thus prepared was transformed to e-caprolactam via cyclohexanone oxime. At present the only industrial process to produce nitroalkanes by direct nitration is the manufacture of nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. 

Polycaproamide (PA-6), which is synthesized from s-caprolactam in the presence of catalysts such as sodium-e-caprolactam or magnesium bromide-caprolactam (obtained by the reaction of... 

Figure 4.1. Flowsheet of production of a reactive mixture by activated anionic s-caprolactam polymerization (explanations of numbers are in the text).

Anionic polymerization of s-caprolactam is used to make cast or RIM polyamide-6. Using a premade lactam chain end and a metal catalyst, it proceeds rapidly at 100-160°C, well below the melting temperature of the polymer, Tm 220°C. The propagation differs from anionic propagation of most unsaturated monomers because the growth center at the chain end is not represented by an anionically activated group but by a neutral N-acy-lated lactam, and the anionically activated species is the incoming monomer (Table 2.26). 

Caprolactam is used principally in the production of nylon 6 fibers. In the production of caprolactam, ammonia is used to maintain a reaction pH of 7 in one step, and in another step ammonia is used to neutralize sulfuric acid. Both of these steps result in the production of a low-grade ammonium sulfate fertilizer. In the classical process 5 kg of (NHO2SO4 are produced per kilogram of caprolactam, hi 1992 about 33% of the worldwide caprolactam capacity was based on DSM s caprolactam process that only produces 1.8 kg of (NH SC per kilogram of caprolactam46. 

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